Metal-containing azo dyestuffs having sulphonyloxy-substituted alkyl sulphone groups



This invention relates to new azo dyestuffs and more particularly itrelates to new metallised azo dyestuffs which are valuable for colouringwool and polyamide textile materials.

According to the invention there are provided the new metallised azodyestuffs which, in the form of the free acids, are represented by theformula:

wherein A and A" each represent substituted or unsubstituted aryleneradicals and may be the same or different, B and B" each represent theresidues of substituted or unsubstituted coupling components whichcouple in the ortho or vicinal positions to D and D" respectively and Band B" may be the same or different, 2' and Z" each represent --O- orCOO and may be the same or different, D and D" each represent -O- or--NH and may be the same or different, M represents a chromium or cobaltatom, R represents a hydrogen atom or a substituted or unsubstitutedalkyl or aryl radical, X represents an alkylene radical, Y represents asubstituted or unsubstituted alkyl or aryl radical, n represents 1 or 2and m represents 1, 2, 3 or 4, provided that each of the groups [SO(NR),, X.OSO Y] is attached directly to a carbon atom present in A, A",B or B" and that A, A", B, B, R, X and Y are free from sulphonic andcarboxylic acid groups.

As examples of the unsubstituted arylene radicals represented by A and Athere may be mentioned monocyclic arylene such as phenylene and bicyclicarylene such as naphthylene and as examples of substituents which may bepresent in these arylene radicals and in the residues of the couplingcomponents represented by B and B" there may be mentioned alkyl forexample lower alkyl such as methyl, alkoxy for example lower alkoxy suchas methoxy, chlorine, bromine, nitro, alkylsulphonyl for examplemethylsulphonyl and ethylsulphonyl, acylamine for example acetylamino,benzoylamino, carbomethoxyamino and carboethoxyamino, sulphamyl andsubstituted sulphamyl for example NzN-dimethylsulphamyl,N-ethylsulphamyl, N-benzoylsulphamyl and N-phenylsulphamyl.

The residues of the coupling components represented by B and B" are theresidues of any coupling components which will couple in the ortho oradjacent position to a hydroxy or amino group, but B and B arepreferably the residues of phenols, naphthols, acylacetarylamides,S-aminopyrazoles or 5-pyrazolones.

As examples of the substituted or unsubstituted alkyl or aryl radicalsrepresented by Y there may be mentioned alkyl radicals for example loweralkyl radicals such as ethyl, propyl and butyl and preferably methyl,which may contain substituents such as a chlorine atom, and as examplesof the aryl or substituted aryl radicals represented by Y there may bementioned substituted and United States Patent 0 unsubstitutedmonocyclic aryl radicals such as phenyl, tolyl, chlorophenyl,methoxyphenyl and nitrophenyl.

As examples of the substituted or unsubstituted alkyl or aryl radicalsrepresented by R there may be men tioned alkyl radicals for examplelower alkyl radicals such as methyl, ethyl, propyl and butyl which maycontain substituents such as hydroxy, methoxy, ethoxy and methanesulphonyloxy groups.

As examples of the alkylene radicals represented by X there may bementioned alkylene radicals containing from 1 to 6 carbon atoms such astrimethylene, methylene, propylene, tetramethylene andazfi-dimethylethylene and preferably ethylene.

According to a further feature of the invention there is provided aprocess for the manufacture of the new metallised azo dyestuffs, ashereinbefore defined, which comprises treating a metallised azo compoundwhich, in the form of its free acid, is represented by the formula:

AN=N B L wherein A, A", B, B", D', D", Z Z", R, X, M, m and n have themeanings stated above, with an acid halide of the formula Y.SO Q whereinY has the meaning stated above, and Q represents a halogen atom.

This process of the invention may be conveniently brought about bytreating a solution of the metallised azo compound in a basic solvent,for example pyridine, with the acid halide, preferably at a temperaturebetween 0 and 35 C., adding water and filtering oflf the metallised azodyestufi which is precipitated.

The treatment of the metallised azo compound with the acid halide mayalso be carried out in aqueous medium in the presence of an acid-bindingagent, for example sodium carbonate, or the treatment may be carried outin an inert organic liquid, for example a hydrocarbon such as toluene,in the presence of an acid-binding agent or a basic organic liquid suchas pyridine.

As examples of acid halides of the formula Y.SO Q which may be used inthis process of the invention there may be mentioned methane sulphonylbromide, ethane sulphonyl chloride, chloromethanesulphonyl chloride,benzene sulphonyl chloride, p-toluene sulphonyl chloride, propanetit-sulphonyl chloride, propane B-sulphonyl chloride, B-methylpropanecad-sulphonyl chloride, p-chlorobenzene sulphonyl chloride, andm-nitrobenzene sulphonyl chloride, but the preferred acid halide ismethane sulphonyl chloride.

The metallised azo compounds used in this process of the invention maybe obtained by treating an azo compound of the formula:

or two different azo compounds of the above formula, wherein Arepresents a substituted or unsubstituted arylene radical, B representsthe residue of a substituted or unsubstituted coupling component whichcouples in the ortho or vicinal position to the group DH, D representsO- or -NH-- and T represents a hydroxy, carboxy or alkoxy group which isattached to A in ortho position to the azo link, provided that A and Bare free from sulphonic acid groups and carboxylic acid groups otherthan a carboxylic acid group represented by T, under mildly acid,neutral or alkaline conditions with an agent or agents yielding chromium0r cobalt in such amounts that correspond to more than 0.5 atomicprodinitro 2 aminophenol,

portions of chromium or cobalt for each molecular proportion of the saidazo compound, the azo compound or compounds being so chosen that theresulting metallised azo compound contains 1, 2, 3 or 4 groups of theformula SO '(-NR),, -'-X-OH, wherein R, X and n have the meanings statedabove.

The azo compounds of Formula I may themselves be obtained'bydiazotis'ing an amine of the formula:

wherein A has the meaning stated above and T represents ahydroxy,carboxy or alkoxy group which is attached to A in ortho position to theamino group, and coupling the diazo compounds so obtained respectivelywith a coupling component of the formula:

which couples in the ortho or vicinal position to the DH group, theamine and the coupling component being so chosen that the resulting azocompounds contain 0, 1 or 2 groups of the formula -SO (NR) XOH whereinR, X and n have the meanings stated above.

As examples of amines which may be used to obtain the azo compounds ofFormula I there may be mentioned o-aminophenol, 4chloro-2-aminophenol,6-chloro- Z-aminophenol, 4-, 5- or 6-nitro-2-aminophenol, 4:6- 4 chloro5 nan) 2 aminophenol; 2-aminophenol-4-sulphonamide, 2-aminophenol 5sulphonamide, 2 aminophenol 4 s sulphon- N B hydroxyethylamide, 2aminophenol 4 sulphondimethylamide, 2 aminophenol 4 sulphonanilide, 2aminophenol 4 sulphon N (3' N B- hydroxyethylsulphamylphenyl) amide,2-aminophenol-4- methylsulphone, 2-aminophenol-4-ethylsulphone,2-aminophenol 4 [9 hydroxyethylsulphone, 2 aminophenol-S-fi-hydroxyethylsulphone, anthranilic acid, 4-chloroanthranilic acid, S-nitroanthranilioacid, anthranilic acid 5-sulphon-N-fl-hydroxyethylamide, anthranilicacid-4-sulphona-mide, anthranilic acid-4-methylsulphone, anthranilicacid-4-fl-hydroxy ethyl sulphone, 4-methoXy-2-aminophenol,4-methyl-2-aminophenol, 2-aminophenol-4-sulphonmorpholide, o-anisidine,4-, 5- or 6-nitro-2-anisidine, 4-, 5- or 6-chloro-2-anisidine,2-aminophenol-4-sulphon-(N- methyl N ,6 hydroxyethyl) amide, 6 nitro 2aminophenol 4 sulphon N ,8 hydroxyethylamide, 2'- aminophenol 4 sulphonN:N di (,8 hydroxyethiyl)amide and6-nitro-l-amino-Z-naphthol-4-sulphonamide.

As examples of coupling components which may be used to obtain the azocompounds of Formula I there may be mentioned S-pyrazolones such asl-phenyl-3- methyl-S-pyrazolone, 1 -(2'-, 3- or 4'-methylphenyl)-3-methyl-S-pyrazolone, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2'-, 3'- or4'-N-/8-h-ydroxyethylsulphamylphenyl)-34rnethyl-5-pyrazolone, 1-(2'-,3'- or 4' [3 hydroxyethylsulphonylphenyl) 3 methyl 5- pyrazolone, l-(2-,3- or 4,-sulphamylphenyl)-3-methyl- S-pyrazolone, 1-(2-, 3'- or4'-nitrophenyl)-3-methyl-5- pyrazolone, 3 methyl 5 pyrazolone, l phenyl5- pyrazolone 3 carboxy 2' methoxy 5' methylanilide,'1-phenyl-5-pyrazolone-3-carboxyanilide, l-phenyl-S- pyrazolone 3carboxy 2' toluidide, 1 (2':5' dichlorophenyl) 3 methyl 5 pyrazolone, 1(2- methoxyphenyl) 3 methyl 5 pyrazolone, 1 (4'-sulphamylnaphthyl)-3-methyl-5-pyrazolone, 1-[3'- or 4'- (N:Ndimethylsulphamyl )phenyl] 3 methyl 5- pyr-azolone, 1-[3'- r4'-(N-methylsulphamy1)phenyl]- 3 methyl pyrazolone, l [3' (N phenyl Nflhydroxyethylsulphamyl)phenyl] '3 methyl 5 pyr azolone and1:3-dimethyl-5-pyrazolone, S-aminopyrazoles such asl-phenyl-3-methyl-5-arninopyrazole, acylacetarylarnides for exampleacetoacetarylides such as acetoactanilide, acetoacet-2-anisidide,acetoacet-4-anisidide, acetoacet-4-chloranilide andacetoacet-Z-toluidide, phenols such as p-cresol, 2:4-dimethylphenol,3:4-dimethylphenol, 2 acetylamino 4 methylphenol and3-acetylamino-4-methylphenol and naphthols such as l benzoylamino 7naphthol, 1 phenylamino 7- naphthol, 1-acetylamino-7-naphthol,1-propionylamino-7 naphthol, 1 benzenesulphonylamino 7 naphthol, 1carbomethoxyamino 7 naphthol, 1 carboethoxyamino 7 naphthol, 1carboisopropoxyamino 7- naphthol, Z-naphthol, 2-nap-lithol-6-sulphon-N-fi-hydroxyethylamide, 2 naphthol 6 Bhydroxyethylsulphone, 2-naphthol-6-sulphonanilide, t2-naphthol-6-sulphonN [4' (N 18 hydroxyethylsulphamyl)phenyl] amide, 6-acetyl-2-naphthol,6-bromo-2-napthol, 1- naphthol 3 sulphonami-de, 1 naphthol 4sulphonamide, 1-naphthol-S-sulphonamide, 2-naphthol-6-sulphonamide,4-acetyl-1-naphthol, 5-chloro-1-naphthol, 5:8-dichloro 1 naphthol, 5:6:7:8 tetrahydro 2 naphthol and 5-:6:7:8 tetrahydro 2 naphthol 3sulphonamide, amines such as 2-naphthylamine andZ-naphthylamine-6-sulphonamide and heterocyclic coupling components suchas 2:4-dihydroxy quinoline, isoquinolinediol and barbituric acid.

According to a further feature of the invention there is provided analternative process for the manufacture of the new metallised azodyestuifs, as hereinbefore defined, which comprises treating 1 or 2diiferent metallisable azo compounds of the formula:

T DH wherein A, B and D have the meanings stated above, and T'represents a hydroxy, carboxy, acyloxy or alkoxy group which is attachedto A in ortho'position to the azo link, with an agent oragents yieldingchromium or cobalt the metallisable azo compound or compounds being sochosen that the resulting metallised azo -dyestuif contains 1, 2, 3 or 4groups of the formula as hereinbefore defined.

The treatment of the metallisable azo compound or compounds'with theagent or agents yielding chromium or cobalt is carried out under mildlyacid, neutral or alkaline conditions, the amount of the agent or agentsyielding chromium or cobalt used'being such that corresponds to'morethan ()5 atomic proportion, and preferably not more than 1.5' atomicproportions, of chromium or cobalt for each molecular proportion of thesaidmetallisable azo compound or compounds.

As examples of the agents yielding chromium or cobalt which maybe usedin the alternative process of the invention there maybe mentionedchromium or cobalt halides, for example the chlorides or fluorides,chromium or cobalt salts of aliphatic carboxylic acids, for exampleformic or acetic acid and mixtures of chromium or cobalt salts withalkali metal salts of aliphatic hydroxycarboxylic acids, for example oftartaric acid, chromium complexesv of aromatic orthohydroxy carboxylicacids, for example salicylic acid.

The treatment of the said metallisable azo compound or compounds withthe-agent or agents yielding chroor cobalt is carried out under mildlyacid, neutral or alkaline conditions. The treatment may be convenientlycarried out at elevated temperature under atmospheric pressures inaqueous medium preferably in the presence of an organic solvent, forexample ethyl alcohol, 'n-butylal'cohol, fi-"ethoxyethanol, ethyleneglycol or acetic acid. The formation'of the metal complex may befacilitated by adding a wetting or dispersing agent to the reactionmixture. Upon completion of the reaction the metallised az'o'dyestuff isseparated and, if desired in the case of those metallised azo dyestulfswhich are solub le in water, may be purified by reprecipitating it, inthe form of a salt from an aqueous alkaline solution, for example an aueous solution rendered alkaline by the addition of sodium carbonate,sodium hydroxide, sodium phosphate or ammonium hydroxide.

The metallisable azo compound or compounds used in the alternativeprocess of the invention may be obtained by treating l or 2 differentazo compounds of Formula I which contain 1 or 2 groups of the formulawith an acid halide of the formula Y.SO Q, wherein R, X, n, Y and Q havethe meanings stated above. When T and/or -DH in the azo compounds ofFormula I represents a hydroxy group then it is believed that the acidhalide also reacts with not more than one of these hydroxy groups togive an acyl group of the formula O.SO Y, but this group is displacedduring the treatment with the agent yielding chromium or cobalt in thealternative process of the invention.

Alternatively the metallisable azo compound or compounds nsed in thealternative process of the invention may be obtained by diazotising anamine of the formula:

A-NH,

J wherein A has the meaning stated above and T represents a hydroxy,carboxy, acyloxy or alkoxy group which is in ortho position to the aminogroup, and coupling the diazo compound with a coupling component of theformula:

as hereinbefore defined, the amine and coupling components being sochosen that the resulting metallisable azo compound contains 1 or 2groups of the formula wherein R, X, Y and n have the meanings statedabove.

As examples of amines containing 1 or 2 groups of the formula -SO (NR)-XO.SO Y as hereinbefore defined, which may be used to obtain themetallisable azo compounds used in the alternative process of theinvention there may be mentioned 4 or S-li-methanesulphonyloxyethylsulphonyl anthranilic acid and 2-methanesulphonyloxy 5(fi-methanesulphonyloxyethylsulphonyl) aniline.

As examples of coupling components containing 1 or 2 groups of theformula SO (NR) -XO.SO Y as hereinbefore defined, which may be used toobtain the metallisable azo compounds used in the alternative process ofthe invention there may be mentioned 1-(3'- or 4'-,B- methanesulphonyloxyethylsulphonylphenyl)-3-methyl-5- pyrazolone.

The new metallised azo dyestuffs, as hereinbefore defined, are ofparticular value for colouring nitrogen-containing textile materials forexample textile materials comprising natural and regenerated proteinfibres such as wool and silk, textile materials comprising syntheticnitrogen-containing fibres for example polyamide fibres such as fibresof polyhexamethyleneadipamide and the polymer of caprolactam,polyurethane fibres and polyacrylonitrile fibres especially modifiedpoly-acrylonitrile fibres. The new metallised azo dyestuffs can also beused for colouring leather.

The new metallised azo dyestuffs, as hereinbefore defined, can beapplied to the textile materials by either a dyeing or a printing paste.For dyeing nitrogen-containing textilernaterials such as wool the newmetallised azo dyestuffs are preferably applied to the said textilematerials from a neutral, acid or slightly alkaline dyebath, preferablyat temperatures between 75 and 120 C. If desired the dye'baths may alsocontain substances which are commonly added when dyeingnitrogen-containing textile materials such as wool, for example sodiumsulphate, ammonium sulphate, acetic acid and formic acid. There may alsobe present in the dyebath anionic surfaceactive agents such as thedisodium salt of methylene dinaphthalene sulphonic acid, non-ionicdispersing agents for example condensates of ethylene oxide with amines,fatty alcohols or alky-lated phenols, and surface-active cationic agentsfor example quaternary ammonium salts such as cetyl trimethylammoniumbromide, cetyl pyridinium bromide and steararnidomethyl pyridiniumchloride. If it is desired to dye the nitrogen-containing textilematerials at temperature below 75 C., for example at temperaturesbetween 40 and 7 5 C. then it is preferred to add a water-solubleorganic liquid, for example a watersoluble alcohol such as butanol orbenzyl alcohol, to the dyebath.

Some of the new metallised azo dyestuffs of the invention have little orno solubility in water and in such cases it is preferred to use thedyestuffs in the form of an aqueous dispersion which may be obtained bymilling the dyestuffs with water in the presence of a dispersing agentsuch as the disodium salt of methylene dinaphthalene sulphonic acid.

The new metallised azo dyestuffs of the invention have excellentafiinity for nitrogen-containing textile materials, especially woollentextile materials, and the colourations so produced have excellentfastness to light and to wet treatments such as washing and inparticular to milling, to potting and to acid cross dyeing.

A preferred class of the new metallised azo dyestuffs are thosedyestufis wherein n represents 1, so that each of the -SO (NR) -XO.SO Ygroup or groups present in the dyestuffs represents the group of theformula SO2-XO.SO2Y, since such dyestuffs give dyeings on wool whichhave better fastness to potting than the new metallised azo dyestuffswherein n represents 2. In this preferred class of dyestuffs Ypreferably represents a methyl radical which can optionally besubstituted by a chlorine atom.

It is believed that the excellent fastness to wet treatments of thecolourations obtained on textile materials from the new premetallisedazo dyestuffs of the invention is due, at least in part, to a chemicalreaction between the dyestuffs and groups such as hydroxy, mercapto oramino groups which are present in the textile materials. It is possiblethat this chemical reaction takes place by alkylation of the saidgroup(s) with simultaneous formation of a sulphonic acid of the formulaY-SOz.OI-I, wherein Y has the meaning stated above, just as methylp-toluene sulphonate is known to be a methylating agent withsimultaneous formation of p-toluenesulphonic acid.

The invention is illustrated but not limited by the following examplesin which the parts and percentages are by weight:

Example 1 A mixture of 40.2 parts of the monoazo compound, which isobtained by coupling diazotised Z-aminophenol- 4-,8-hydroxyethylsulphone with IphenyI-B-methyl-S-pyrazolone in the presence of sodiumcarbonate, 14.5 parts of chromium acetate and 500 parts of 50% aqueousalcohol is heated at the boil under a reflux condenser untilmetallis-ation of the monoazo compound is complete. The solution soobtained is poured into a 10% aqueous solution of sodium chloride andthe metallised azo compound which is precipitated is filtered off anddried.

A mixture of 43.7 parts of the above metallised azo compound, 12.5 partsof methane sulphonyl chloride and 300 parts of pyridine is stirred for 5hours at a temperature of between 0 and 5 C. The solution so obtained ispoured onto a mixture of 200 parts of ice and 300 parts of water and 50parts of sodium chloride are then added. The precipitated dyestuff isthen filtered off and dried.

The new chromium-containing azo dyestuff so obtained when applied towool from a neutral or weakly acid dyeba-th yields orange shades whichhave excellent fastness properties to washing, milling, potting,acid-cross dyeing, rubbing and to light.

Example 2 In place of the 43.7 parts of the metallised azo compound usedin Example 1 there are used 54.4 parts of the metallised azo compoundwhich is obtained by treating with an aqueous solution of chromiumacetate the monoazo compound obtained by coupling diazotisedZ-aminophenol-4-ethyl sulphone with 1-(4'-B-hydroxyethylsulphamylphenyl-3 -methyl-S -py=razolone.

The new chromium-containing azo dyestuir" so obtained when applied towool from a neutral or weakly acid dyebath yields orange shadespossessing excellent fastness to Wet treatments and to light.

Example 3 In place of the 43.7 parts of the metallised azo compound usedin Example 1 there are used 51.6 par-ts of the metallised azo compound.which is obtained by treating with an aqueous solution of chromiumacetate the monoazo compound obtained by coupling diazotized2-aminophenol-4-me-thyl sulphone with 1-(4-,8-hydroxyethylsulphonylphenyl)-3-methyl-5-pyrazolone. 1

The new chromium-containing azo dyestuff so obtained when applied towool from a neutral or Weakly acid dyebath yields orange shadespossessing excellent fastness to wet treatments and to light.

Example 4 Example 5 In place of the 43.7 parts of the metallised azocompound used in Example 1 there are used 49.0 parts of the metallisedazo compound which is obtained by treating with an aqueous solution ofchromium acetate the monoazo compound obtained by coupling diazotised 2-aminophenol 4-p-hydroxyethyl sulphone wit-hl-carbethoxyamino-7-naphthol.

The new chromium containing azo dyest-ufi so obtained when applied towool from a neutral or weakly acid dyebath yields grey shades possessingexcellent fastness to wet treatments and to light.

Example 6 In place of the 43.7 parts of the metallised azo compound usedin Example 1 there are used 28 parts of the metallised azo compoundwhich is obtained by treating with an aqueous solution of chromiumacetate the monoazo compound obtained by coupling diazotised2-aminophenol 4 ,8 hydroxyethylsulphone with 1 (3-fi-hydroxyethylsulphamylphenyl -3 -methyl-5 -pyrazolone.

The new chromium-containing azo dyestufi so obtained when applied toWool from a neutral or weakly acid dyebath yields orange shadespossessing excellent fastness to wet treatments and to light.

Example 7 In place of the 43.7 parts of the metallised azo compound usedin Example 1 there are used 50 parts of the metallised azo compoundwhich is obtained by treating with an aqueous solution of cobalt acetatethe monoazo compound obtained by coupling diazotised5-nitro-2-aminophenol with 1(4-,8hydroxyethylsulphamylphenyl)-3-methyl-Spyrazolone.

The new cobalt-containing azo dyestufl so obtained when applied from aneutral or weakly acid dyebath yields bordeaux shades possessingexcellent fastness to wet treatments and to light. 7

Example 8 e A mixture of 42.9 parts of the monoazo compound obtained bycoupling diazotised 2-aminophenol-4- 3hydroxyethyl sulphone with1-ac-tylamino-7-naphthol, 25 parts of methane sulphonyl chloride and 200parts of pyridine is stirred for 5 hours at a temperature of between 0and 5 C. The solution so obtained is poured onto ice and theprecipitated solid is filtered oil, washed with water and dried. Thesolid so obtained is dissolved in 300 parts of ethanol, 132 parts of anaqueous solution of sodium/potassium chromosalicylate (which is obtainedas described in Example 2 of British specification No. 787,305) areadded and the mixture is stirred at the boil under a reflux condenserfor 2 hours. The solution so obtained is poured into parts of a 20%aqeous solution of sodium chloride and the dyestulf which isprecipitated is filtered oft and dried. The chromium-containing azodyestufl. so obtained is identical with the dyestuff obtained asdescribed in Example 4.

The following table gives further examples of the new metallised azodyestuffs of the invention which are obtained by the methods describedin Examples 1 to 8 except that the monoazo compounds used in these examples are replaced by an equivalent amount of the monoazo compounds usedin these examples are replaced by an equivalent amount of the monoazocompound which is obtained by diazotising the amine listed in the secondcolumn of the table and coupling with the coupling component listed inthe third column of the table. The fourth column of the table lists themetal (chromium or cobalt) which is present in the dyestuff, and thefifth column of the table gives the shade obtained when the dyestufi isapplied to a woolen textile material.

Shade obtained on Ex A ine Coupling component Metal woolen textilematerials 14- -h drox eth lsul hone1-pheny1-5-pyrazolone-3-carboxy-m-chloranilide Ohromium Red. if KEg B yp l-phenylamin0-7-naphthoL. Cobalt Olive. 0 p-Ores l o Redclish-brown.'iI amino henol 1:(3-fl-hsidroxyethylsulphonyl-phenyl)-3-methy1-5-Chrormunn. Red.

' pyrazo one.

' -5- nlnnnnamido do do Red. ii" f 'f} .do Cobain..." Orange. I 1 1 -2-mmo heno1 1-(4aft-bradr0xyethylsulphonyl-phenyl)-3-methyl-5-Chl'OIHlllm-.. Bed.

' pyrazo one. 16" 4-nitro-2-aminophen0ldo do Orange. 72-a,mjn0phen0l-4-methylS111Ph0I1B 18-.6-nitr0-1-amin0-2-naphtho1-4:sulphm1a e I .do Reddish-brown. g 23minophenol-5-sulphonamide do Red. 20" dn Cobalt Orange. 21 2+ i hnolt-fl-hydroxyethyl-sulphOne Acet acet-p-chlof p do Yellow. doAcetoaeet-o-tol nd dp d D 23 Acetoacet-p-amslmd do Do. 1Acet0acet-m-4-xyl1dide .do Do. 3-acetamido-p-cresol Chromium" Brown. 25"(in l-phenyl-S-methyl-fi-pyrazolone Cobalt Reddish-yellow. dn1-(3-ehlorophenyl)-3-methy1-5-pyrazo1one '-.do Do. 28: -d0 do Ghromlurm-Orange.

In place of the 12.5 parts of methanesulphonyl chloride used in Example1 there are used 14.2 parts of ethanesulphonyl chloride whereby adyestutf is obtained which 12 dyes-tuft is then filtered oil and dried.The dyestuff so obtained when applied to wool from a neutral or slightlyacid dyebath yields brown shades which possess excellent ,tastnes twashing. t mi ng and t l g thas similar properties to the dyestufi ofExample 1. 5 Example 135 The following table gives further examples ofthe new In place of the 19.3 parts of the monoazo compound dyestuffs ofthe invention which are obtained by the obtained by coupling4-chlor-2-aminophenol with l-carmethod described in Example 1 exceptthat (a) the 43.7 boethoxyarnino-7-naphthol used in Example 134 thereparts of the metallised azo compound used in Example 1 are used 24 partsof the monoazo compound obtained are replaced by an equivalent amount ofthe metallised 10 by coupling diazotised Z-aminophenol-4-e-hydroxyethylazo compound which is obtained by diazotising the amine sulphone with2-naphthol-G-B-hydroxyethyl sulphone and listed in the Second column ofthe table, coupling with in place of the 6.3 parts of methane sulphonylchloride the coupling component listed in the third column oi the thereare used 18.9 parts of methane sulphonyl chloride table and treating theaz o compoundso obtained with a whereby a dyestuft is obtained whichdyes wool from a metallising agent of the metal (chromium or cobalt)neutral or slightly acid dyebath in brown shades which listed in thefourth column of the table and (b) the 12.5 possess excellent fastnessto washing, to milling and to parts of methane sulphonylchloride used inExample 1 light. are replaced by an equivalent amount of the sulphonylThe 2-aminophenol-4-fl-hydroxyethylsulphone used in chloride listed inthe fifth column of the table. The sixth the above examples may beobtained in the form of its column of the table indicates the shadeobtained when hydrochloride by the following method: the dyestuff isapplied to a woolen textile material. A mixture of 220.5 parts of1-chlorobenzene-4-5-hy- Ex. Amine Coupling Component Metal sulphonylchloride Shade 123 2-a15inopheno1-4-B-hydroxy-ethylsull-(3methylphenyl)-3-methyl-5-pyrazolone Chromium" Ethanesulphonylchlorlde.-. Orange.

p 0116' 124 o 2-naphthol-6-sulphonamlde Cobalt .-do Bordeaux. 125 2amlnophenol 4 sulphon N fl l-phenyl-3-methyl-5-pyrazolone. ChromlunndoOrange.

' hydroxyethylamide 126.- d0 l-carboethoxyamino-7-naphthol do d0 Grey.127-- 2manigophenol-4 fl-hydroxyethyll-phenyl-3-methyl-5-pyraz0loncdo... B-Ifgluene sulphonyl chlo- Orange.

sup 0118 Il. e 128 do 1-acetylamino-7-nanhthol do do Grey. 129--2-aminophenol-4 sulphon-NzN-di B-Naphtholr o do Brownish-(fl-hydroxyethyhamide violet. 130-. do do Cobalt do Bordeaux. 131--2-aminophenol-4-B-hydroxy-ethyl fi-Tetralol Chromium Chloromethanesulphonly Brown.

sulphone chloride 132" .do 1-(2-ch1oropheny1)-3-methyl-5-pyrazodom-Nitrobenzene sulphonyl Orange.

' lone chloride Example 133 Diazotised2-aminophenol-4-,S'-hydroxyethylsulphone is coupled with1-(2z5-dichlonophenyl)-3-methyl-5-pyrazclone and the monoazo compound soobtained is heated with a solution of chromium acetate in a mixture ofethanol and water to yield the 1:2-chromecomplex.

A mixture of 52.15 parts of the above chrome complex and 500 parts oftoluene is stirred at the boil .and 100 parts of toluene are allowed todistill oif from the mixture. The mixture is then cooled to 10 C. and 50parts of pyridine and 12.5 parts of methane sulphonyl chloride areadded. The mixture so obtained is then stirred for 20 hours at atemperature between 5 and 10 C. and the'precipitated dyestuif is thenfiltered off, washed with benzene and dried.

The dyestult so obtained when applied to wool from a neutral or slightlyacid dyebath yields orange shades possessing excellent fastness to wettreatments and to light.

Example 134 A mixture of 20.1 parts of the monoazo compound obtained bycoupling diazotised 2-aminopheno1-4-p-hydroxyethyl sulphone with1-phenyl-3-methyl-5-pyrazolone, 19.3 parts of the monoazo compoundobtained by coupling diazotised 4-chlor-2-aminophenol withl-carboethoxyamino-7-naphthol, 500 .parts of ethanol, 500 partsofethylene glycol, 200 parts of water and 14.5 parts of chromium acetateisistirredat theboil under a reflux condenser for 16 hours. The solutionso obtained is cooled to 20 C., 400 parts of a 10% aqueous solution ofsodium chloride are added and the dyestutf which is precipitated isfiltered off and dried.

A mixture of the above metallised compound, 6.3 parts of methanesulphonyl chloride and 400 parts of pyridine is stirred for 20 hours ata temperature between 10 and 15 C. The solution so obtained is thenpoured into a mixture of 400 parts of ice and 400 parts of water and.8r0.pa ts..o f sodiumchloride areadded. Th pre ipitated.

droxyethylsulphone and 441 parts of sulphuric acid is stirred at atemperature between 20 and 25 C. for 15 hours. 73 parts of nitric acid(of specific gravity 1.5) are then slowly added during 2 to 3 hours, thetemperature of the mixture being maintained between 20 and 25 C. byexternal cooling, and the mixture is then stirred for a further 15 hoursat the same temperature. The mixture is then slowly added, withstirring, to 3500 parts of ice and water, sufficient ice being presentto ensure that the temperature of the resulting mixture does not exceed10 C. The mixture so obtained is then filtered, the filtrate is cooledto 5 C. and 400 parts of potassium chloride are added. The mixture isthen stirred for 3 hours at atemperature of 5C. and the potassium saltof phone are slowly added to a mixture of parts of iron powder, 10 partsof acetic acid and 750 parts of water which is stirred at the boil undera reflux condenser and the mixture so obtained is then stirred for afurther 4 hours at the boil. 97 parts of a 32% aqueous solution ofsodium hydroxide are then added and the mixture is filtered. 200 partsof a concentrated aqueous solution of hydrochloric acid are added to thefiltrate and the mixture so obtained is cooled to 15 C. when thehydrochloride of 2- aminophenol-4-;3-hydroxyethyl sulphone crystallisesout and is filtered oif and dried.

The 2 -n aphthol-6-fi-hydroxyethylsulphone used in the above examplesmay be obtained by treating 2-naphthol- 6-:sulphonic acid with p-toluenesulphonchloride in aqueous medium, converting the resulting2-p-toluenesulphonyloxynaphthalene-6-sulphonic acid to the correspondingsulphonchloride by treatment with phosphorus oxychloride, reducing thesulphonchloride to the sulphinic acid, with an aqueous solution ofsodium sulphite, treating the sulphinic acid with ethylenechlorohydrinin aqueous medium in the presence of sodium carbonate, and finallyheating with an aqueous solution of sodium carbonate to hydrolyse offthe p-toluenesulplronyl group.

The anthranilic acid 4-[3-hydroxyethylsulphone used in the aboveexamples may be obtained by reacting p-toluenesulphinic acid withethylenechlorohydrin in aqueous medium in the presence of sodiumcarbonate, nitrating the resulting p-toluene-fl-hydroxyethylsulphone,oxidising the resulting 3-nitr-o-4-methylbenzene [ii-hydroxyethylsulphone with an aqueous solution of potassium permanganate to yield3-nitro-4-carboxybenzene ,8-hydroxyethylsul phone and finally reducingthe nitro group to an amino group by an aqueous iron reduction.

The 2-aminophenol-S-B-hydroxyethylsulphone used in the above examplesmay be obtained by treating 2-aminophenol with phosgene, reacting theresulting benzisoxazolone with chlorosulphonic acid to form thesulphonylchloride, treating with an aqueous solution of sodium sulphiteto fiorm the sulphinic acid, condensing with ethyl ene chlorohydrin inaqueous medium in the presence of sodium carbonate and finally heatingwith a dilute aqueous solution of sodium hydroxide.

The 1-(3'- or 4'-fl-hydroxyethylsulphonylphenyl)-3- meth-S-pyrazolonesused in the above examples may be obtained from3'-fl-hydroxyethyl-sulphonylaniline and 4'-,8-hydroxyethylsulphonylaniline respectively by diazotising, reducing toform the hydrazine and subsequently condensing with ethylacetoacetate inthe presence of sodium hydroxide.

What We claim is:

Metallized azo dyestutfs which are represented by the formula:

14 wherein:

A and A" respectively stand for a member selected from the groupconsisting of phenylene and naphthylene radicals;

5 B and B respectively stand for a coupling component selected from theclass consisting of phenols, naphthols, acylacetarylamides,S-aminopyrazoles, 5- pyrazolones, and 2:4-dihydroxyquinoline;

and any substituents on the radicals A, A", B, and B are selected fromthe class consisting of lower alkyl,

lower alkoxy, chlorine, bromine, nitro, lower alkyl sulfonyl,acetylamino, propionylamino, benzoylamino, carbomethoxyamino,carboethoxyamino, carboisopropylamino, snlfamyl, N :N-dimethylsulfamyl,N-ethylsulfamyl, N-benzoylsulfamyl, N-phenylsulfamyl, N-methylsulfamyl,N-isopropylsulfamyl, N:N-diethylsulfarny1, acetyle, and phenylamino;

Z and Z" respectively stand for a member selected from the classconsisting of --O and COO-;

D and D" respectively stand for a member selected from the groupconsisting of -O- and -NH-;

M is a metal selected from the group consisting of chromium and cobaltions;

-X is an alkylene radical having from 1 to 6 carbon atoms;

Y is a member selected from the class consisting of lower alkyl, chlorolower alkyl, phenyl, tolyl, chlorophenyl, methoxyphenyl, andnitrophenyl;

m is one of the numbers 1, 2, 3, and 4;

each -SO XOSO Y group is attached directly to a carbon atom of one of A,A, B, and B".

References Cited in the file of this patent UNITED STATES PATENTS2,826,572 Kuster et a1. Mar. 11, 1958 FOREIGN PATENTS 1,002,099 GermanyFeb. 7, 1957 OTHER REFERENCES Wegmann, Textil-Praxis, October 1958,pages 1056- 1058, 260-144. (Copy available in Scientific Library.)

